MODES OF OCCURRENCE OF TRACE ELEMENTS IN COAL by Robert B. Finkelman This report was originally submitted to the Chemistry Department, University of Maryland, in partial fulfillment of the requirements for the degree of Doctor of Philosophy, 1980. U. S. Geological Survey. OPEN FILE REPORT. This report is preliminary and has not been edited or reviewed for conformity with Geological Survey standards or nomenclature. Any trade names are used for descriptive purposes only and do not constitute endorsement by the U. S. Geological Survey. ABSTRACT Modes of Occurrence of Trace Elements in Coal by Robert Barry Finkelman The chemical and physical environment (mode of occurrence) of the trace elements in coal can influence their behavior during the cleaning, conversion, or combustion of the coal, and during the weathering of leaching of the coal or its by-products. Information on the mode of occurrence of the trace elements is, therefore, essential for the efficient use of our coal resources. Previous attempts to determine the mode of occurrence of the trace elements in coal have been largely indirect. Results of the most commonly used appproach, sink-float separation, is often contradictory. Evidence obtained from this study indicate that results from sink-float separations are susceptible to gross misinterpretations. In order to directly determine the mode of occurrence of the trace elements in coal, a tehcnique was developed using the scanning electron microscope (SEM) with an energy dispersive (EDX) detector. This analytical system allows the detection and analysis of in-situ, micron-sized minerals in polished blocks of coal. In addition, mineralogical data were obtained from individual particles extracted from the low-temperature ash of the coal. These techniques were applied in an in-depth study of the Waynesburg and Upper Freeport coals, both bituminous coals from the Appalachian Basin. In addition, brief studies were conducted on about 80 coals representing every rank and type, and every major coal basin in the United States plus about 20 coals from worldwide locations. The results indicate that many trace elements in coal can occur quantitatively in micron-sized accessory mineral grains scattered throughout the organic matrix (macerals). For example, Zn and Cd occur predominantly in the mineral sphalerite; Cu in chalcopyrite; Zr and Hf in zircons; the REE, Y, and Th in monazite and xenotime. In Appalachain Basin coals, lead selenides are dominant over lead sulfides, whereas outside the Basin, lead sulfides are far in excess over the selenides. The majority of the lead in coal, however, may be substituting in barium-bearing minerals. Some elements, such as As and Hg, occur in solid solution with pyrite. The difference in the mode of occurrence between As and Hg and the other chalcophile elements is reflected in their behavior during sink-float separation of the coal; those elements forming micron-size minerals within the macerals are concentrated in the lighter Sp. G. fractions; whereas, those elements associated with pyrite are concentrated in the heavier Sp. G. fractions. Organic associations constitute a major mode of occurrence for several trace elements. Although Ti-bearing minerals are common in many coals, no more than about 50 weight percent of the Ti can be accounted for in this manner. The remainder is probably bound to the organics. Similarly, significant amounts of Se and Br appear to be organically bound. The mode of occurrence of uranium is quite complex; in one sample, virtually all the U occurred as micron-sized grains of uraninite; in another a significant amount of the U was associated with detrital accessory minerals such as zircon; in other coals, the bulk of the U appeared to be organically bound. This study demonstrated that the SEM-EDX system can be used to rapidly characterize the accessory minerals in most coal samples. The information so generated provides direct knowledge of the modes of occurrence of many trace elements in coal. Some of these trace elements appear to have been quite mobile at some time during the coalification process. This study also demonstrated that, although some elements are inoganically bound in coal, during fractionation, they behave as if they are organically bound. It is evident that this type of detailed analytical approach is essential if we are to anticipate accurately the effects of the trace elements on the various technological processes that coals will undergo. ii Acknowledgements I owe a deep debt of gratitude to Harry J. Rose, Jr., and Irving A. Breger both of the U. S. Geological Survey and the Urn*verity of Maryland. They freely offered much needed advise and encouragment through the duration of this study. I would also like to extend my sincere thanks to the many individuals who have rendered assistance at various stages of this study. Among these are: Drs. Isidore Adler and Sheldon Sommer of the University of Maryland; Peter Zubovic, C. Blaine Cecil, and Ronald W. Stanton, of the U. S. Geological Survey. My deepest appreciation is reserved for my wife and children, whose unwavering support has been invaluable. iii Table of Contents Page Acknowledgements.................................... 11 Table of contents................................... 111 List of Tables...................................... v11 List of Figures..................................... 1x Section 1. Introduction............................ 1 1.1 Samples................................. 3 1.2 Analytical Techniques................... 13 1.21 Scanning Electron Microscopy (SEM). 13 1.211 Sample Preparation for SEM... 18 1.22 Low-Temperature Ashing............. 20 1.23 X-ray Diffraction.................. 21 1.24 Electron Microprobe Analysis....... 22 1.25 Transmission Electron Microscopy... 23 1.26 Ion Microprobe Analysis............ 23 1.27 "Lexan" Technique.................. 24 1.28 Chemical Analysis.................. 25 1.3 Separation Techniques................... 25 1.31 Size Separations................... 26 1.32 Magnetic Separations............... 27 1.33 Heavy-Liquid Separations........... 27 Section 2. Results................................. 31 2.1 Minerals in Coal........................ 31 2.11 Introduction....................... 31 2.12 Variety of Accessory Minerals in Coal............................... 33 IV 2.121 Accessory Minerals in the Waynesburg Coal............. 34 2.1211 Results from SEM Study of Polished Blocks............. 34 2.1212 Results from LT ash Residues 37 2.122 Comparison of the Waynesburg Coal Data to Data from Other Coals....................... 42 2.13 Frequency of Occurrence of Accessory Minerals................................ 45 2.131 Minerals Not Previously Reported in Coal............ 47 2.14 Comparison of Accessory Minerals by Coal Rank, Age, and Type..................... 47 2.141 Comparison by Rank.......... 48 2.142 Comparison by Age........... 49 2.143 Comparison by Coal Type..... 49 2:15 Comparison of Accessory Minerals by Geographic Region..........'............. 49 2.16 Variation of Accessory Minerals within a Coal Column........................... 50 2.17 Concentration of Accessory Minerals 1n Coal................................. 51 2.171 Introducti on................ 51 2.172 Relative Abundance of Accessory Minerals.......... 52 2.173 Quantification of Accessory Phases and Their Relationship to Trace Elements........... 54 2.18 Mode of Occurrence of Accessory Sulfide and Selenide Minerals................... 60 2.181 Introducti on................ 60 2.182 Results from Current Study.. 61 2.183 Di scussion.................. 72 2.2 Relationship Between Minerals and Macerals................................. 75 2.21 Introduction........................ 75 2.22 Application of the SEM.............. 76 2.23 Results from Current Study.......... 78 2.24 Mineralogy of Microcleats........... 88 2.3 Sink-Float Experiments................... 92 2.31 Introduction........................ 92 2.32 Sink-Float Separation of the Waynesburg Coal..................... 93 2.33 Sink-Float Separation of the Waynesburg LT Ash................... 94 2.34 Sink-Float Separation of the Upper Freeport Coal................. 95 2.35 Discussion of Sink-Float Separations 95 Section 3. Discussions.............................. 102 3.1 Source of Inorganic Elements and Minerals in Coal.................................. 102 3.11 Introduction........................ 102 3.12 Origin of Minerals in Coal.......... 104 3.2 Modes of Occurrence of Trace Elements.... 110 3.21 Introduction........................ 110 3.211 Sink-Float Separations - Literature Review............. 112 3.212 Variation of Trace Element Con­ centration with Ash Content... 116 3.213 Leaching Characteristics...... 118 3.214 Correlation Coefficients...... 119 3.22 Modes of Occurrence................. 121 3.23 Concluding Remarks.................. 243 3.3 Mode of Occurrence - Geochemical and Technological Considerations.................. 243 3.31 Geochemical Considerations................ 244 3.32 Technological Considerations.............. 247 Section 4. Summary and Conclusions........................ 250 Appendix I Coal Petrographic Nomenclature Used in This Report.................................... 256 Appendix II List of Minerals in Coal....................... 259 Appendix III Chemical Analyses A. INNA Analyses of Sink-Float Samples from the Waynesburg Coal............................ 260 B. OES Analyses of Sink-Float Samples from the Waynesburg Coal............................ 262 C. INNA Analyses of Sink-Float Samples